Process for the production of neutrally developable textile prints



PROCESS FOR THE PRODUCTION OF NEUTRALLY DEVELOPABLE TEXTILE PRINTS Albert Bolleter, Muttenz, and Eduard Moser, Basel,

Switzerland, assignors to Ciba Limited, Basel, Switzerland, a firm of Switzerland No Drawing. Filed Aug. 24, 1956, Ser. No. 605,935 Claims priority, application Switzerland Aug. 25, 1955 15 Claims. (Cl. 3-71) This invention relates to a process for the production of neutrally developable textile prints.

, For the production of water-insoluble azodyestufis on the fiber by printing on of customary coupling components and stabilized diazo compounds with the addition of salts of halogen-fatty acids and alkalies to the printing pastes and development of the dyestufi by steaming with neutral steam, it is already known to use labile diazoamino-compounds with solubilizing groups in the stabilizer, as are obtained by combination of negatively substituted amines with stabilizers of weak basic character or of positively substituted amines with stabilizers of more strongly basic character, together with alkali salts of halogen-fatty acids and alkali in a quantity of at most 1-2 mols. calculated on the quantity of the coupling component.

The present invention is based on the observation that in some cases the use of alkali salts of halogenated fatty acids is not at all necessary and that textile prints devel opable with neutral steam and of equal value can be obtained in the absence of halogen-fatty acid salts. In the process of the invention there are used a customary cou- 1 pling component for the manufacture of ice-colors, alkali in a quantity of preferably more than 2 mols, calculated on the quantity of the coupling component used, and a labile diazoamino compound of the general formula in which Y indicates a sulfonamide group which is preferably disubstituted, more especially by alkyl groups, Z is a low molecular, branched alkyl radical and X is a group of the composition C -NH-Aryl Pater-ma man 19st in which the aryl radical is, for example, a naphthalene radical or a radical of the benzene series, such as a phenyl-, 2-, 3- or 4-methylphenyl-, 2- or 4-methoxyphenyl-, 2- or 4-ethoxyphenyl-, 4-chloro-2-methylphenyl-, 2 5 -dimethoxy-4-chlorophenyl-, 2 4-dimethoxy-5-chlorophenyl-, 2:6-dimethylphenylor 2-methyl-4-methoxyphenyl radical.

The diazoamino-compounds to be used together with the specified coupling components for the manufacture of the printing preparations to be used in the present process, can be obtained by methods known per se, for

example by condensation of a diazotized aromatic base free from water-solubilizing groups, of the general formula in which the symbols X and Y have the same significance as in Formula 1 above, with an aminobenzene carboxylie acid-sulfonic acid of the general formula (3) EN sonar 00011 in which Z indicates a low molecular, branched alkyl radical, preferably an isopropyl or an isobutyl radical. The condensation advantageously takes place in an alkaline medium, and the resulting alkali salts of the diazoamino-compounds can easily be isolated by methods known per se, for example by salting out or by subjecting a solution thereof, if desired after filtration, to a rapid drying process. There may be primarily mentioned as suitable aromatic bases, free from water-solubilizing groups, of the Formula 2, those containing a sulfonamide group of which the nitrogen atom is attached on one side to the SO -group and on the other side to a carbon atom of an alkyl group and to a hydrogen atom or to two carbon atoms of a single aliphatic chain, if desired interrupted by hetero atoms, or preferably to one carbon atom of each of two low molecular alkyl radicals. As examples of such bases of the Formula 2, thefollowing may be especially mentioned:

1-aminobenzene-3-sulfonic acid piperidide, 1 1-amino-2-methoxybenzene-S-sulfonic acid diethylamide, 1-amino-2-methoxybenzene-S-sulfonic acid dimethylamide, 1-amino-2-methylbenzene-S-sulfonic acid diethylamide, l-amino-2-methylbenzene-5-sulfonic acid dimethylamide, 1-amino-2-methylbenzene-5-su1fonic acid morpholide, l-amino-Z-methylor -methoxybenzene-S-sulfonic acid piperidide, 1-amino-2-methoxybenzene-5-sulfonic acid morpholide, l-amino-Z-methoxyor -methylbenzene-S-sulfonic acid isopropyl amide.

The printing preparations are produced from the specified components with the addition of the customary solvents and thickening agents. There are advantageously used in the present process printing preparations of the specified type to which a free alkali metal hydroxide, for example sodium or potassium hydroxide, has been added in such quantities that in the printing preparation, to 1v mol of coupling component more than 1 mol, preferably 2.1 to 5 mols of free alkali metal hydroxide are present. The resulting printing preparations are stable. 7

By means of the present process there can be printed uniform and mixed fabrics, especially such as consistof,

cellulose fibers, using any customary method, for examplefilm or roller printing. Color fast prints are thus obtained on neutral or acid steaming in the absence of the specified' halogen-fatty acid salts. In many cases, the printed 10 minutes at 40-50 C. with an enzymepreparation. Then cold rinsing is repeated, followed by 10 minutes soaping at the boil, repeated rinsing and drying. Clean, full prints are obtained. The same printing eifect is fabric, pre-dried in the customary manner, can be de- 6 also obtained when instead of neutral steaming, acid veloped by heating to temperatures above 100 C.,-prefe rsteaming is carried out for 2-5 minutes at 100 C.

ably 130-150 C. This can be; carried out, for example, The diazoamino-compound required for the manufacm electrically or otherwise heated chambers without the ture of printing paste A can be prepared as follows:

pp y f For this P p there must e added 24.2 parts of 1-amino-2-rnethylbenzene-S-sulfondiethylto the Prmtlllg Pastas Small quantltles 0f hydfophlllc 10 amide are diazotized in the customary manner in 45 stances.f0reX1mp1eglver01- parts of 10% hydrochloric acid and 30 parts "of ice The followlng P F Illustrate the lnvemlon, with 6.9 parts of sodium nitrite in parts of water.

Parts and P g belng y Welght E Otherwise At the same time 28.5 parts of i-isopropyl-aminostated i relation between P by weight P Pa benzene-Z-carboxylic acid-4-sulfonic acid are dissolved in by u bemg same as that between the kflogram 15 200 parts of water with the equivalent quantity of and the sodium hydroxide solution and 60 parts of potassium Eaxmples carbonate are also added. As soonas the whole is d's- Printing preparations are made up containing in h solved, the solution is cooled to 0 C. and the filtered 100 parts, the quantities of ingredients set forth in the 20 diazo solution 18 added dropwise within 20 minutes with following table: good stirring. After a short time, the diazoamino- Diazoamino-compound fromg Sodium di- Titre, Sodium isooronyl- Shade of Example percent Parts Coupling component Parts sulfate nanhthaprint Base Stabilizer lene sulfonate A l-Amlno-Z-methyll-Isonronyl-amino- 70 57.0 1-(2z3hydroxy- 26.5 15.5 1.0 yellowish benze e-5-sulionbenzene-Z-carboxynanhthoyll-aminored. diethyl-amldo. lie acid-@sulfonic 2:5-dlmethoxy-4- acid. chloro-benzene.

B 1-Amino-2-methyl- 1-Isobutylnminohen 60 71.2 dn 27.8 1.0 bluish benze e-i-sulfonzene-2-earboxylic scarlet. dimethylamide. acid 4-su1fon1c acid. 7

C l-Amino z-methyldo 74.4 1-(2:3-hy r0Xy- 21.5 3.1 1.0 orange;

be\'1z'en'e-5-sulfoII- nanhthoyD-aminomornholide. zeth'oxy benzene.

D; 1-Amino-2-m'ethoizy do 78 56:8 1-(2:3-hy r0Xy- 29.4 12.8 1.0 bluish benzene-fi-sulfonnaohthoyli-arninored.

diethyiamide. 2:4-dimeth0Xy-5 chimeenzene;

E; l-AminoQ-rnethyldo 65' 62.1 3-hydrocycarbazole- 25.2 11.7 1 0 fawn,

beuze'm-S-sulion- Z-carboxylic aeid nineri iide. 4-chloranilide.

F, '1-Amino-2-methyld0 60 62.0 l-Acetoacetylamino- 27 2 9. 8 1 0 golden benze eisnlfom 4-benzoyiaminoyellow. diethylamide; 2:5-diethoxybenze e.

G 1-Amino-2-methyll-Isonrooylamino- 55. 68.8 1-(2;3"-hydro'xy- 2312 7.0 1.0 yellow benze e-fi-sulfonbenzene-2-carbox' nanhthoyD-aminoorange. piperidide. yiiitzl acid-4-sulionio 2 ethoxy benzene.

H". i-amino-z-methoxy- 1-Isnbutylamin0ben- 73.2 .....(10 24.1 1.7 1.0 redbenzene-S-sulfouzene-Q-carboxylie orange. dimethyl-amide. acidt-sulfonic acid.

I; l-Amino-Z-methoxydo 80 71.1 l-Acetoacetyl-amino- 23.0 4.9 1.0 green benzene-S-sulion- 4-acetyl-amino-2- yellow. morpholide. chloro-fi-methoxybenzene. it no l-Isopropyl-amino- 55' 74.3 1-(2':3-hydroxynaph- 22.1 2.6 1.0 red.

benzene-2-carboxthoyD-amino-2- ylieI aeid-4-su1fonie methow-benzene. 801

L 1-Amino-2-methoxy- I-Isohutyl-arnino- 55 73.2 1-(2:3'-hydroxynaph- 23 7 2.1 1 0 bluish red.

benzene-5-sulfonbenzene-Z-carboxthoyD-amino-Z- isopropyl-amide. yiic acid-4-suiionie methyi-4-oh1oroacid. benzene.

With. these printing preparations, printing pastes are compound crystallizes in fine'leaflets and after 2 hours made up as follows: the coupling is complete. For completion of the separa- A B C D E F G H I K L Printing pre aration- 80 80 80 60 80 80 60 80 80 Denatured alcohQL... 30 30 30 20 50 50 50 50 50 50 Thiodiethylene glycol- 50 50 Urea 30 Sodium di-iso-nropyl-naphthalenesultonate,10%so1ution 20 20 20 30% Sodium hydroxide solution-... 20 20 15 20 15 15 20 15 15 20 20 Water 300 330 285 310 275 285 280 285 305 280' 280 Neutral Starch Tragacanth-Thick- Turpentine 10 10 10 10 10 10 10 10 10 10 10' 1,000 1, 000 1,000 1, 000 1,000 1,000 1,000 1,000 1.000 1, 000 1,000

A cotton fabric is printed with these pastes. The printed material is dried at 50-60 C. and then subjected to neutral steaming in a Mather and Platt steamer for 58 minutes at C. Cold rinsing: is then carried out tion, 10 volumes percent of sodium chloride are further added, stirring is continued for 1 hour and then the well defined crystalline precipitate is filtered with suction. It is washed with a little saturated sodium chloride solu-.

followed by treatment for removal of" the starch for" 75 tion, pressed off and dried under vacuum at 45-50 C.

.The diazoamino-compound obtained in good yield has a content of 65-70% and is easily soluble in water.

By this method there can be obtained from the corresponding diazoamino-compounds in yields of 75-85% of the theoretical; they have similar propertfes. The diazoamino-compound used for the production of the printing preparation C was obtained as follows:

A diazo solution prepared in the customary manner from 25.6 parts of 1-amino-2-methylbenzene-S-sulfonmorpholide of the formula is introduced dropwise within 20 minutes into a solut'on of 31.7 parts of the disodium salt of l-isobutylaminobenzene-Z-carboxylic acid 4-sulfonic acid, 2 parts of anhydrous sodium carbonate and 2 parts of sodium bicarbonate in 300 parts of water, cooled to 0 to minus 2 C. At the same time so much 30% sodium hydroxide solution is added dropwise that the pH value of the mixture continuously amounts to 9.5-10. It is finally adjusted to and the whole filtered from a little impurity and the solution evaporated in a spray drier, the entry temperature of the air being between 130 and 180 C. and the exit temperature not less than 70 C. and not considerably more than 100 C.

The resulting fine, yellowish powder has a content of about 50% of diazoamino-compound. The yield amounts to 80-85% of the theoretical.

.Bythis method there can be obtained from (a) 27.2 parts of 1-amino-2-methoxybenzene-S-sulfonmorpholide and 30.3 parts of the disodium salt of 1 isopropylaminobenzene-2-carboxylic acid-4-sulfonic acid,

(b) 27.2 parts of 1-amino-2-methoxybenzene-5-sulfonmorpholide and 31.7 parts of the disodium salt of l-isobutylaminobenzene 2 carboxylic acid-4-sulfonic acid,

(0) 23.0 parts of 1-amino-2-methoxybenzene-S-sulfon-dimethylamide and 31.7 parts of the disodium salt of l-isobutylaminobenzene 2 carboxylic acid-4-sulfonic acid,

(d) 25.4 parts of 1-amino-2methylbenzene-S-sulfon-piperidide and 30.3 parts of the disodium salt of H50- propylaminobenzene-Z-carboxylic acid-4-sulfonic acid,

(e) 24.4 parts of l-amino-Z-methoxybenzene-S-sulfonisopropylamide and 31.7 parts of the disodium salt of l-isobutylaminobenzene 2 carboxylic acid-4-sulfonic acid,

the corresponding diazoamino-compounds in yields of 80-85% of the theoretical; they have similar propertles.

What is claimed is: 1. In a process for the production of a water-insoluble azo dyestulf on the fiber by printing on of a coupling component and a stabilized diazo compound and develop ment of the dyestuff by steaming with steam at a pH not above neutrality, the improvement of carrying out said process, in the absence of halogen fatty acids and their salts, with a coupling component suitable for the manufacture of ice-colors, an alkali in a quantity of more than 2 mol calculated on the quantity of the coupling component used and a labile diazo-amino compound of the formula 0 nn-1C uHfln'H.

N=N1IT SOaH O O H in which Y is an alkylated sulfonamide group, Z is a low molecular, branched alkyl radical having at most 4 C atoms and m and n are each a positive whole number of which the product is at most 2.

2. In a process for the production of a water-insoluble azo dyestufi on the fiber by printing on of a coupling component and a stabilized diazo compound and development of the dyestuif by steaming selectively with neutral steam and with acid steam, respectively, the improvement of carrying out said process, in the absence of halogen fatty acid and their salts, with a coupling component suitable for making ice colors and a labile diazo-amino compound of the formula COOH in which Y is an alkylated sulfonamide group, Z is a low molecular branched alkyl radical having at most 4 C atoms and m and n are each a positive whole number of which the product is at most 2, and a quantity of 2.1 to 5 mols of free alkali hydroxide per one mol of the coupling component.

3. In a process for the production of a water-insoluble azo dyestufi on the fiber by printing on of a coupling component and a stabilized diazo compound and development of the dyestufi by steaming selectively with neutral steam and with acid steam, respectively, the improvement of carrying out said process, in the absence of halogen fatty acids and their salts, with a coupling component selected from the group consisting of the arylides of acetoacetic acid, of 2-hydroxy-carbazole-3-carboxylic ac:'d and of Z-hydroxy-naphthalene-3-carboxylic acid, 2.1-5 mole of alkali hydroxide per one mol of coupling component and a labile diazo-amino compound of the formula 1 COOH in which Y is an alkylated sulonamide group, Z is a low molecular, branched alkyl radical having at most 4 C atoms and m and n areeach a positive whole number of which the product is at most 2.

4. In a process for the production of a water-insoluble azo dyestufi on the fiber by printing on of a coupling component and a stabilized'diazo compound and develop-. ment of the dyestuif by steaming selectively with neutral steam and with acid steam, respectively, the improvement of carrying out said process, in the absence of halogen fatty acids and their salts, with a coupling component selected from the group consisting of the arylides of moses 7 aceto acetic acid, of 2-hydroxy-carbazole-3-carboxylie acid and of Z-hydroxynaphthalene-B-carboxylic acid, 2.1- mols of an alkali hydroxide per mole of coupling component and a labile diazo-amino compound of the formula SOQX wherein m and n each represent a whole number of at most 2.

5. In a-proeess for the production of a water-insoluble azo dyestufi on the fiber by printing on of a coupling component and a stabilized diazo compound and development of the dyestuff by steaming selectively with neutral steam and with acid steam, respectively, the improvement of carrying out said process, in the absence of halogen fatty acids and their salts, with a coupling component selected from the group consisting of the anilides of aceto acetic acid, of Z-hydroxy-carbazole-3-carboxylie acid and of Z-hydroxynaphthalene-3-carboxylic acid, 2.1- 5 mols of an alkali hydroxide per mol of coupling component and a labile diazo-amino compound of the formula mit-1C n tim SOQX in which Z is a member selected from the group consisting of the isopropyl and isobutyl radicals and X stands for one of the radicals m ZmH C m 2m+1 C H: C H:

CnHIuq CHQCH:

and

OHZCHL' CHzC'H:

wherein m and n each represent a whole number of at most 2.

6. In a process for the production of a water-insoluble azo dyestuff on the fiber by printing on. of a coupling component and astabilized diazo compound and development of the dyestufi by steaming selectively with neutral 8 a steam and with acid steam, respectively, the improvement 'of carrying out said process, in the absence of halogen fatty acids and their salts, with the coupling component of the formula on 0011, CONHOC1 ()CHs the diazo-amino compound of the formula CH3 CH:

SOIN

and 2.15 mols of an alkali hydroxide per mol of the coupling component.

7. In a process for the production of a water-insoluble azo dyestufi on the fiber by printing on of a coupling component and a stabilized diazo compound and development of the dyestuff by steaming selectively with neutral steam and with acid steam, respectively, the improve ment of carrying out said process, in the absence of halogen fatty acids and their salts, with the coupling component of the formula wort CONHOC! i the diazo'amino compound of the formula CH; CH;

ment of the dyestuff by steaming selectively with neutral steam and with acid steam, respectively, the improvement of carrying out said process, in the absence of halogen fatty acids and their salts, with the coupling component of the formula court the diazo amino compound of the formula and 2.1- mols of an alkali hydroxide per mol of cou pling component.

9. A printing preparation which is free from halogenated fatty acids and their salts and contains a coupling component suitable for the manufacture of ice-colors. an alkali in a quantity of more than 2 mols calculated on the quantity of the coupling component used and a labile diazo-amino compound of the formula in which Y is a alkylated sulfonamide group, Z is a low molecular, branched alkyl radical having at most 4 carbon atoms and m and n are each a positive whole number of which the product is at most 2.

10. A printing preparation containing a labile diazoamino compound of the formula in which Y is a alkylated sulfonamide group, Z is a low molecular, branched alkyl radical having at most 4 carbon atoms and m and n are each a positive whole number of which the product is at most 2 and instead of halogen fatty acids or their salts a quantity of 2.1 to 5 mols of free alkali hydroxide per one mol of the coupling component present in the preparation.

11. A printing preparation which is free from halogenated fatty acids and their salts and contains a coupling component selected from the group consisting of the arylides of acetoacetic acid, of 2-hydroxy-carbazole-3- carboxylic acid and of 2-hydroxynaphthalene-3-carboxylic acid, 2.1-5 mols of alkali hydroxide per one mol of coupling component and a labile diazo-amino compound of the formula COOH in which Y is an alkylated sulfonamido group, Z is a low molecular, branched alkyl radical having at most 4 carbon atoms and m and n are each a positive whole number of which the product is at most 2.

12. A printing preparation which is free from halogenated fatty acids and their salts and contains a coupling component selected from the group consisting of the arylides of acetoacetic acid, of 2-hydroxy-carbazole-3- carboxylic acid and of 2-hydroxynaphthalene-3-carboxylic acid, 2.1-5 mols of an alkali hydroxide per mol of coupling component and a labile diazo-amino compound of the formula in which Z is a member selected from the group con- 10 sisting of the isopropyl and isobutyl radicals and Xstands for one of the radicals wherein m and it each represent a whole number of at most 2.

13. A printing preparation which is free from halogenated fatty acids and their salts and contains a coupling component selected from the group consisting of the anilides of acetoacetic acid, of 2-hydroxy-carbazole-3- carboxylic acid and of Z-hydroxynaphthalene-3-carboxylic acid, 2.1-S mols of an alkali hydroxide per mol of coupling component and a labile diazo-amino compound of the formula 0 Ill-1C nHInH in which Z is a member selected from the group consisting of the isopropyl and isobutyl radicals and X stands for one of the radicals,

m flnH C H2m+i 011105:

omen,

and

CHQCHI \CH: oHtoa wherein m and n each represent a whole number of at most 2.

14. A printing preparation which is free from halm genated fatty acids and their salts and contains the coupling compound of the formula CHsCOCHaC ONH- NHCOCHS OCH:

the diazo-compound of the formula CH: CH;

CH OCH: H

COOH CHsC a CHzCH:

SOQN

and 2.1-5 mols of an alkali hydroxide per mol of coupling component.

pling component of the formula 15. A erintin'g preparation which is mafia!!! halo; and 21-5 molsof an alkali hydroxide per molof con genated fatty acids and their salts andcont'aius the cou-- plingcomponent, r I

References Cited in the file of this patent 0H I 1 UNITED STATES PATENTS V 2,758,001 Glietenberg Aug. 7, 1956 G I 2,781,337 Moser et a]. Feb. 12, 1957 2,781,338 MOSer Feb. 12, 1957 e -ammo compound of the formula r 2,822,234 Breig Feb. 1958 CH: CH: 10

:i FOREIGN PATENTS E 1,058,960 France Mar. 22, 1954 3 1,067,249 France June 14, 1954 N=NN 501E {5 OTHER REFERENCES Cm OOH I 'Lubs: The Chem. of Synthetic Dyes and Pigments, g f Reinhold Pub. Co., N'.Y., 1955, pp. 203-204. eo,NHc V r 1 r Y Jour. Soc. Dyers and Co., July 1955, pp. 418-419.

UNITED STATE 5' PATENT OFFICE CERTIFICATIQN 0F CORRECTION Patent No 2,910,030 4 January 51Y 1961 Albert Bolleter et, a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 17, for "Eaxmples", in italics read Examples in italics; columns 3 and first table thereof, column 6, line 13 thereof for "3-hydrocycarbazole" read 3hydroxycarbazole column 6, line 64, for "sulonamide" read sulfonamide column 7 lines 15 and 54, and column 10, lines 1 and 35,for "radicalsV, each occurrence read radicals and m and n are each a positive nlhole number of which the product is at most 2 Signed and sealed this 10th day of April 1962 (SEAL) Attest:

ERNEST? w; rzswraefi DAVID L. LADD 'A the s-t-i:n.1o1" f i C e r Commissioner of Patents 

1. IN A PROCESS FOR THE PRODUCTION OF A WATER-INSOLUBLE AZO DYESTUFF ON THE FIBER BY PRINTING ON OF A COUPLING COMPONENT AND A STABILIZED DIAZO COMPOUND AND DEVELOPMENT OF THE DYESTUFF BY STEAMING WITH STEAM AT A PH NOT ABOVE NEUTRALITY, THE IMPROVEMENT OF CARRYING OUT SAID PROCESS, IN THE ABSENCE OF HALOGEN FATTY ACIDS AND THEIR SALTS, WITH A COUPLING COMPONENT SUITABLE FOR THE MANUFACTURE OF ICE-COLORS, AN ALKALI IN A QUANTITY OF MORE THAN 2 MOL CALCULATED ON THE QUANTITY OF THE COUPLING COMPONENT USED AND A LABILE DIAZO-AMINO COMPOUND OF THE FORMULA 